Cyclohexane derivatives having plant-growth regulating activities, and uses of these derivatives

ABSTRACT

As new compound is provided a cyclohexane derivative of the formula ##STR1## wherein R represents a hydrogen atom or an alkyl group, an alkylthioalkyl group or an unsubstituted or substituted phenyl group; and R 1  represents an alkyl group, an unsubstituted or substituted benzyl group, a phenethyl group, a phenoxymethyl group, a 2-thienylmethyl group, an alkoxymethyl group or an alkylthiomethyl group, or a salt of said cyclohexane compound. 
     This cyclohexane compound exhibits useful plant-growth regulating effects on crop-plants and also non-crop plants such as lawn and may be prepared by cyclization of an acetonylsuccinic acid dialkyl ester, followed by reaction with an organic acid chloride and by intermolecular rearrangement.

HISTORY OF THE APPLICATION

This application is a division of U.S. application Ser. No. 534,827filed Sept. 22, 1983, now U.S. Pat. 4,560,403 issued Dec. 24, 1985.

FIELD OF THE INVENTION

This invention relates to a new cyclohexane derivative, moreparticularly a new derivative of 3,5-dioxo-cyclohexanecarboxylic acid,having high plant-growth regulating activities and to a process for thepreparation of said cyclohexane derivatives. This invention also relatesto a plant-growth regulating composition comprising said cyclohexanederivative as the active ingredient, and further to a method ofregulating the growth of a plant using said cyclohexane derivative.

BACKGROUND OF THE INVENTION

Various chemical compounds have been used for regulation of the growthof plants with a chemical substance, so called for the purpose of"chemical control" of plantgrowth. For example, maleic hydrazide (MH),N,N-dimethylaminosuccinic amide (known as Daminozide or B-Nine) and2-chloroethyl trimethyl ammonium chloride (known as Chlormequat or CCC)have been employed for retardation of plant-growth, for control ofemergence of sideshooting or for prevention of lodging of plants. Theseknown compounds, however, have various drawbacks such as: a. their useis restricted with respect to the locus, plants and time which caneffectively be treated with them, b. their plant-growth regulatingeffects are insufficient or unstable, c. they are phytotoxic, and/or d.they are too expensive.

We have made extensive studies in an attempt to provide new plant-growthregulators which are free from the aforementioned drawbacks of the knownplant-growth regulators. As a result, we have now found that certain newcyclohexane derivatives, which we have now newly synthetized, exhibitsome remarkable plant-growth regulating effects and are free from thedrawbacks as described above.

DETAILED DESCRIPTION OF THE INVENTION

According to an aspect of this invention, therefore, there is provided acyclohexane compound of the general formula: ##STR2## wherein Rrepresents a hydrogen atom or an alkyl group, an alkylthioalkyl group oran unsubstituted or substituted phenyl group; and R¹ represents an alkylgroup, an unsubstituted or substituted benzyl group, a phenethyl group,a phenoxymethyl group, a 2-thienylmethyl group, an alkoxymethyl group oran alkylthiomethyl group, or a salt of said cyclohexane compound.

The alkyl group which R may represent in the general formula (I)includes those containing 1 to 8 carbon atoms, for example, methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,n-pentyl, and iso-pentyl groups.

The alkyl group which R¹ may represent includes those of 1 to 8 carbonatoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,n-pentyl, n-hexyl, n-heptyl and n-octyl groups.

The substituent on the substituted phenyl group which R may represent,as well as the substituent on the substituted benzyl group which R¹ mayrepresent may be a lower alkyl group of 1 to 4 carbon atoms such asmethyl; halo group such as chloro; and a lower alkoxyl group of 1 to 4carbon atoms such as methoxy.

Typical examples of the cyclohexane compounds of the general formula (I)are listed in Table 1 below, where the physical properties of eachcompound are also indicated.

                  TABLE 1                                                         ______________________________________                                         ##STR3##                      (I)                                            Com-                                                                          pound                             Physical                                    No.   R           R.sup.1         Properties                                  ______________________________________                                         1    C.sub.2 H.sub.5                                                                           CH.sub.3        m.p.                                                                          40˜42° C.                       2    n-C.sub.3 H.sub.7                                                                          "              m.p.                                                                          43˜44° C.                       3    i-C.sub.3 H.sub.7                                                                          "              m.p.                                                                          98˜100° C.                      4    n-C.sub.4 H.sub.9                                                                          "              n.sub.D.sup.20 = 1.4991                      5    i-C.sub.4 H.sub.9                                                                          "              m.p.                                                                          39˜40° C.                       6    s-C.sub.4 H.sub.9                                                                          "              m.p.                                                                          36˜37° C.                       7    t-C.sub.4 H.sub.9                                                                          "              m.p.                                                                          76˜77° C.                       8    CH.sub.3    C.sub.2 H.sub.5 m.p.                                                                          49˜50° C.                       9    C.sub. 2 H.sub.5                                                                           "              m.p.                                                                          55˜56° C.                      10    n-C.sub.3 H.sub.7                                                                          "              n.sub.D.sup.20 = 1.4960                     11    i-C.sub.3 H.sub.7                                                                          "              m.p.                                                                          55˜56° C.                      12    H            "              m.p.                                                                          98˜99° C.                      13     "          n-C.sub.3 H.sub.7                                                                             m.p.                                                                          116˜119° C.                    14    CH.sub.3     "              n.sub.D.sup.20 = 1.5025                     15    C.sub.2 H.sub.5                                                                            "              m.p.                                                                          34˜35° C.                      16    n-C.sub.3 H.sub.7                                                                          "              n.sub.D.sup.20 = 1.5010                     17    i-C.sub.3 H.sub.7                                                                          "              n.sub.D.sup.20 = 1.4941                     18    n-C.sub.4 H.sub.9                                                                          "              n.sub.D.sup.20 = 1.4930                     19    i-C.sub.4 H.sub.9                                                                          "              n.sub.D.sup.20 = 1.4958                     20    s-C.sub.4 H.sub.9                                                                          "              n.sub.D.sup.20 = 1.4893                     21    i-C.sub.5 H.sub.11                                                                         "              n.sub. D.sup.20 = 1.4885                    22                                                                                   ##STR4##    "              m.p. 91˜92° C.                 23                                                                                   ##STR5##    "              m.p. 123˜124° C.               24                                                                                   ##STR6##    "              m.p. 115˜116° C.               25    C.sub.2 H.sub.5                                                                           i-C.sub.3 H.sub.7                                                                             n.sub.D.sup.20 = 1.4898                     26     "          n-C.sub.4 H.sub.9                                                                             n.sub.D.sup.20 = 1.4943                     27     "          i-C.sub.4 H.sub.9                                                                             n.sub.D.sup.20 = 1.4948                     28     "          n-C.sub.5 H.sub.11                                                                            n.sub.D.sup.20 = 1.4878                     29     "          n-C.sub.6 H.sub.13                                                                            n.sub.D.sup.20 = 1.4803                     30     "          n-C.sub.7 H.sub.15                                                                            n.sub.D.sup.20 = 1.4773                     31     "          n-C.sub.8 H.sub.17                                                                            n.sub.D.sup.20 = 1.4650                     32     "                                                                                         ##STR7##       m.p. 67˜68°  C.                33     "                                                                                         ##STR8##       m.p. 80˜81° C.                 34     "                                                                                         ##STR9##       m.p. 66˜68° C.                 35     "          C.sub.2 H.sub.5 OCH.sub.2                                                                     n.sub.D.sup.20 = 1.5035                     36     "          C.sub.2 H.sub.5 SCH.sub.2                                                                     n.sub.D.sup.20 = 1.5357                     37    H           CH.sub.3        m.p.                                                                          139˜141° C.                    38    CH.sub.3     "              m.p.                                                                          77˜77.5° C.                    39    t-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5 m.p.                                                                          67˜69° C.                      40    CH.sub.3 SC.sub.2 H.sub.4                                                                 n-C.sub.3 H.sub.7                                                                             n.sub.D.sup.20 = 1.5170                     41    C.sub.2 H.sub.5                                                                            ##STR10##      m.p. 74˜75° C.                 42     "                                                                                         ##STR11##      m.p.  78˜79° C.                43     "                                                                                         ##STR12##      n.sub.D.sup.20 = 1.5610                     44     "                                                                                         ##STR13##      m.p. 61˜63° C.                 ______________________________________                                    

Amongst the particular compounds of Table 1, the following compounds arepreferred in this invention.

(1) Compound No. 8: 3,5-dioxo-4-propionylcyclohexanecarboxylic acidmethyl ester;

(2) Compound No. 9: 3,5-dioxo-4-propionylcyclohexanecarboxylic acidethyl ester;

(3) Compound No:10: 3,5-dioxo-4-propionylcyclohexanecarboxylic acidn-propyl ester;

(4) Compound No.13: 3,5-dioxo-4-butyrylcyclohexanecarboxylic acid;

(5) Compound No.15: 3,5-dioxo-4-butyrylcyclohexanecarboxylic acid ethylester;

(6) Compound No.16: 3,5-dioxo-4-butyrylcyclohexanecarboxylic acidn-propyl ester;

(7) Compound No.17: 3,5-dioxo-4-butyrylcyclohexanecarboxylic acidisopropyl ester;

(8) Compound No.18: 3,5-dioxo-4-butyrylcyclohexanecarboxylic acidn-butyl ester;

(9) Compound No.21: 3,5-dioxo-4-butyrylcyclohexanecarboxylic acidisopentyl ester;

(10) Compound No.25: 3,5-dioxo-4-isobutyrylcyclohexanecarboxylic acidethyl ester; and

(11) Compound No.37: 3,5-dioxo-4-acetylcyclohexanecarboxylic acid.

For plant-growth regulators to be applied onto grass swards, it isusually required that they should have a particularly improved saftetyin their stimulus for human's skin and eye since they are frequentlyused for treatment of swards planted in golf links, parks or yards sothat they are likely to be brought into direct contact with humanbodies.

Through our further studies, we have found that such a class of the newcyclohexane derivative of the general formula (I) which is representedby the following general formula (Ia) ##STR14## wherein R² represents ahydrogen atom or an alkyl group and R³ represents an alkyl group canprovide such a salt with an inorganic or organic cation which exhibits asignificantly reduced stimulus to skin and eye of the animal or human,as compared to the similar salt of the another classes of the newcyclohexane derivative according to the general formula (I), withretaining their excellent plant-growth regulating effects.

According to a preferred embodiment of the first aspect of thisinvention, therefore, there is provided a salt of a cyclohexane compoundof the general formula: ##STR15## wherein R² represents a hydrogen atomor an alkyl group and R³ represents an alkyl group.

The salt of the new cyclohexane compound according to the generalformula (Ia) may be any of the following three types:

(i) A salt of the cyclohexane compound represented by the generalformula: ##STR16## wherein R² and R³ are as defined above and Mrepresents an organic or inorganic cation.

(ii) A salt of the cyclohexane compound represented by the generalformula: ##STR17## wherein R³ and M are as defined above.

(iii) A salt of the cyclohexane compound represented by the generalformula: ##STR18## wherein R³ and M are as defined above.

In the above formulae (Ia), (Ib), (Ic) and (Id), R.sup. is as definedhereinbefore and preferably is a hydrogen atom or an alkyl group such asmethyl, ethyl, n-propyl, iso-propyl, n-butyl or iso-butyl, R.sup. is asdefined hereinbefore and preferably is an alkyl group such as mentionedjust above, and M stands for an organic or inorganic cation. Theinorganic cation here may be the cation of an alkali metal (includingammonium cation), an alkaline earth metal, aluminium, copper, nickel,manganese, cobalt, zinc, iron and silver. The organic cation may be asubstituted ammonium ion represented by the formula: ##STR19## whereinR⁴, R⁵, R⁶ and R⁷ each represents a hydrogen atom or an alkyl, ahydroxyalkyl, an alkenyl, benzyl, a halogen-substituted benzyl, pyridylor an alkyl-substituted pyridyl group, or R⁴ and R⁵ taken together forma polymethylene group which may optionally be interrupted by an oxygenatom.

Typical examples of the various salts of the formula (Ib), (Ic) or (Id)according to this invention are shown in Tables 2-4 below.

                                      TABLE 2                                     __________________________________________________________________________     ##STR20##                             (Ib)                                   Compound No.                                                                          R.sup.2                                                                           R.sup.3                                                                           M             Physical Properties                             __________________________________________________________________________    45      CH.sub.3                                                                          CH.sub.3                                                                          H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                              m.p. 88˜91° C.                     46      "   C.sub.2 H.sub.5                                                                   "             m.p. 85˜86° C.                     47      "   "                                                                                  ##STR21##    m.p. 90˜92° C.                     48      "   n-C.sub.3 H.sub.7                                                                 H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                              m.p. 62˜64° C.                     49      C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          "             (see Table 5 given later)                       50      "   "   H.sub.2 N.sup.⊕ (C.sub.2 H.sub.5).sub.2                                                 (see Table 5)                                   51      "   C.sub.2 H.sub.5                                                                   "             (see Table 5)                                   52      "   "   H.sub.2 N.sup.⊕ (n-C.sub.3 H.sub.7 ).sub.2                                              m.p. 76˜80.5° C.                   53      "   "   H.sub.2 N.sup.⊕ (i-C.sub.3 H.sub.7).sub.2                                               m.p. 42˜44.5° C.                   54      "   "   H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                              m.p. 76˜78° C.                                                   (see Table 5)                                   55      "   "                                                                                  ##STR22##    m.p. 91˜94° C.                     56      "   "   H.sub.2 N.sup.⊕ (CH.sub.2 CHCH.sub.2).sub.2                                             (see Table 5)                                   57      "   "   H.sub.2 N.sup.⊕ (n-C.sub.4 H.sub.9).sub.2                                               m.p. 94˜96° C.                     58      "   "   H.sub.2 N.sup.⊕ (i-C.sub.4 H.sub.9).sub.2                                               (see Table 5)                                   59      "   "                                                                                  ##STR23##    refractive index n.sub.D.sup.25 = 1.4965        60      "   "   H.sub.2 N.sup.⊕ (n-C.sub.12 H.sub.25                                                    m.p. 62˜63° C.                     61      "   "                                                                                  ##STR24##    m.p. 63˜65° C.                     62      "   "   H.sub.3 N.sup.⊕ (t-C.sub.4 H.sub.9)                                                     refractive index                                                              n.sub.D.sup.20 = 1.5069                         63      "   "   HN.sup.⊕ (C.sub.2 H.sub.5).sub.3                                                        refractive index                                                              n.sub.D.sup.25 = 1.5098                         64      "   "   HN.sup.⊕ (C.sub.2 H.sub.4 OH).sub.3                                                     m.p. 53˜56° C.                     65      "   "                                                                                  ##STR25##    refractive index n.sub.D.sup.25 = 1.5505        66      "   "                                                                                  ##STR26##    m.p. 55˜56° C.                     67      "   "                                                                                  ##STR27##    m.p. 55˜57° C.                     68      "   "                                                                                  ##STR28##    m.p. 75˜76° C.                     69      "   "                                                                                  ##STR29##    m.p. 67˜68° C.                     70      "   "   1/2 Mg.sup.2⊕                                                                           m.p. 184˜188° C.                   71      "   "   1/2 Cu.sup.2⊕                                                                           m.p. 203˜206° C.                                                 (decomp.)                                       72      "   "   1/2 Ni.sup.2⊕                                                                           m.p. >290° C.                            73      "   "   1/2 Ca.sup.2⊕                                                                           (see FIG. 1)                                    74      "   "   Na.sup.⊕  (see FIG. 2)                                    75      "   "   K.sup.⊕   (see FIG. 3)                                    76      "   n-C.sub.3 H.sub.7                                                                 H.sub.2 N.sup.⊕ (C.sub.2 H.sub.5).sub.2                                                 m.p. 63˜65° C.                     77      "   "   H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                              m.p. 51˜53° C.                     78      "   "   Na.sup.⊕  (see FIG. 4)                                    79      "   "   K.sup.⊕   (see FIG. 5)                                    80      "   "   1/2 Ca.sup.2⊕                                                                           m.p. 157˜159° C.                   81      "   "   1/3 Fe.sup.3⊕                                                                           refractive index                                                              n.sub.D.sup.20 = 1.5475                         82      "   "   1/3 Al.sup.3⊕                                                                           refractive index                                                              n.sub.D.sup.20 = 1.5294                         83      i-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                              m.p. 71˜73° C.                     __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR30##                    (Ic)                                            Com-                                                                          pound                           Physical                                      No.   R.sup.3 M                 Properties                                    ______________________________________                                        84    n-C.sub.3 H.sub.7                                                                     HN.sup.⊕ (C.sub.2 H.sub.5).sub.3                                                            refractive index                                                              n.sub.D.sup.20 = 1.5182                       85    "       (HOC.sub.2 H.sub.4)N.sup.⊕ (CH.sub.3).sub.3                                                 refractive index                                                              n.sub.D.sup.20 = 1.5118                       86    "       H.sub.2 N.sup.⊕ (C.sub.2 H.sub.5).sub.2                                                     refractive index                                                              n.sub.D.sup.20 = 1.5172                       87    "       H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                                  refractive index                                                              n.sub.D.sup.20 = 1.5330                       88    C.sub.2 H.sub.5                                                                       H.sub.3 N.sup.⊕ (n-C.sub.3 H.sub.7)                                                         (see FIG. 6)                                  89    "                                                                                      ##STR31##        refractive index n.sub.D.sup.20 = 1.5392      90    "       H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                                  refractive index                                                              n.sub.D.sup.20 = 1.5283                       91    "       Na.sup.⊕      m.p. 225° C.                                                           (decomp.)                                     92    "       K.sup.⊕       m.p. 200˜205° C.                 ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR32##                    (Id)                                            Compound                                                                      No.     R.sup.3 M            Physical Properties                              ______________________________________                                        93      C.sub.2 H.sub.5                                                                       Na.sup.⊕ m.p. 240° C. (decomp.)                    94      "       H.sub.2 N.sup.⊕ (C.sub.2 H.sub.4 OH).sub.2                                             refractive index                                                              n.sub.D.sup.20 = 1.5351                                                       (see FIG. 7)                                     95      n-C.sub.3 H.sub.7                                                                     Na.sup.⊕ refractive index                                                              n.sub.D.sup.20 = 1.5261                          ______________________________________                                    

In the accompanying drawings, FIGS. 1, 2, 3, 4, 5, 6 and 7 show infraredabsorption spectra of Compound Nos. 73, 74, 75, 78, 79, 88 and 94,listed in Tables 2-3, resectively.

Table 5 below shows the analytical results of nuclear magnetic resonancespectra (in CDCl₃) of some of the compounds according to this inventionwhich are indicated with reference to Compound Number as shown in Tables2-3.

                  TABLE 5                                                         ______________________________________                                        Com-                                                                          pound Characteristic peaks for particular radicals                            No.   in N.M.R. Spectra                                                       ______________________________________                                        49                                                                                   ##STR33##                                                                     ##STR34##                                                                     ##STR35##                                                                     ##STR36##                                                                     ##STR37##                                                                     ##STR38##                                                              50                                                                                   ##STR39##                                                                     ##STR40##                                                                     ##STR41##                                                                     ##STR42##                                                                     ##STR43##                                                                     ##STR44##                                                              51                                                                                   ##STR45##                                                                     ##STR46##                                                                     ##STR47##                                                                     ##STR48##                                                              54                                                                                   ##STR49##                                                                     ##STR50##                                                                     ##STR51##                                                                     ##STR52##                                                                     ##STR53##                                                                     ##STR54##                                                              56                                                                                   ##STR55##                                                                     ##STR56##                                                                     ##STR57##                                                                    H.sub.2 N.sup.⊕: s, 2H, 10.0 ppm                                           ##STR58##                                                                     ##STR59##                                                                     ##STR60##                                                              58                                                                                   ##STR61##                                                                     ##STR62##                                                                     ##STR63##                                                                     ##STR64##                                                                     ##STR65##                                                                     .sub.--H.sub.2 N.sup.⊕: s, 2H, 8.16 ppm                                   ##STR66##                                                              ______________________________________                                    

Amongst the particular compounds of Tables 2-4, the following compoundsare preferred in this invention.

(12) Compound No.54: [Bis-(2-hydroxyethyl)]ammonium salt of ethyl3,5-dioxo-4-propionylcyclohexanecarboxylate.

(13) Compound No.74: Sodium salt of ethyl3,5-dioxo-4-propionylcyclohexanecarboxylate.

(14) Compound No.93: Di-sodium salt of3,5-dioxo-4-propionylcyclohexanecarboxylic acid.

(15) Compound No.94: Bis-{[bis-(2-hydroxyethyl)]ammonium} salt of3,5-dioxo-4-propionyl-cyclohexanecarboxylic acid.

(16) Compound No.55: [Bis-(2-hydroxypropyl)]ammonium salt of ethyl3,5-dioxo-4-propionylcyclohexanecarboxylate.

The compounds of the general formula (I) can be prepared by a methodbriefly depicted according to the following reaction equations:##STR67## wherein R and R¹ are as defined hereinabove for the generalformula (I) and M' is an alkali metal.

The 3,5-dioxo-cyclohexanecarboxylic acid alkyl ester alkali metal saltof the above formula (III) may be prepared by reacting anacetonylsuccinic acid di-alkvl ester compound of the formula (II) with abasic reagent in a suitable solvent. This cyclization reaction can becarried out at a temperature ranging from room temperature to theboiling point of the solvent used for a period of 1 to 10 hours. Thebasic reagent to be used in this reaction includes an alkali metalalcoholate such as sodium methylate, sodium ethylate and potassiumtert-buthoxide or an alkali metal hydride such as sodium hydride.Examples of the solvent used here may be methanol, ethanol, benzene,toluene, xylene, N,N-dimethylformamide, dimethylsulfoxide anddimethylcellosolve.

The 3,5-dioxo-cyclohexanecarboxylic acid or its alkyl ester compound ofthe formula (IV) can be made by treatment of the compound (III) preparedas above with an acid such as hydrochloric acid.

The compound of the above formula (VI) can be prepared by condensing thecompound (III) or (IV) in an inert organic solvent with an organic acidchloride of the formula (V) where R¹ is as defined hereinbefore, in thepresence or absence of γ-picoline and in the presence or absence of abase. This condensation reaction may be carried out at a temperature inthe range from -20° C. to the boiling point of the solvent when used,and preferably at or below ambient temperature. The reaction time mayvary from 10 minutes to 7 hours depending upon the reaction conditionsemployed. The base which may optionally be used in this reactionincludes any of such acid-binding agents which are generally employedfor the conventional dehydrohalogenation, for examples, organic basessuch as trimethylamine, triethylamine, diethylamine, dimethylamine orpyridine and inorganic bases such as sodium or potassium hydroxide. Thesolvent available for this reaction may include water and/or organicsolvents such as toluene, benzene, xylene, dichloromethane,1,2-dichloroethane, chloroform, carbon tetrachloride,N,N-dimethylformamide, dimethylsulfoxide and methylcellosolve. Thiscondensation reaction is conveniently performed with the aid ofγ-picoline which will act as phase transition catalyst when using waterand organic solvent as the reaction medium.

The new compound of the formula (I) according to this invention can beproduced by subjecting the intermediate compound of the above formula(VI) to a rearrangement reaction in the presence of a catalyst and anorganic solvent at a temperature from room temperature to the boilingpoint of the solvent for a period of 1 to 10 hours. The catalyst to beused for this rearrangement reaction includes pyridine derivatives suchas 4-N,N-dimethylaminopyridine, 4-N,N-diethylaminopyridine and4-pyrolidinoaminopyridine; or N-alkylimidazole derivatives such asN-methylimidazole and N-ethylimidazole.

The new compound (I) of this invention can be prepared without isolationor purification of said intermediate compounds (III), (IV) and (VI).

According to a second aspect of this invention, therefore, there isprovided a process for the production of a cyclohexane compound of thegeneral formula (I): ##STR68## wherein R represents a hydrogen atom oran alkyl group, an alkylthioalkyl group or an unsubstituted orsubstituted phenyl group; and R¹ represents an alkyl group, anunsubstituted or substituted benzyl group, a phenethyl group, aphenoxymethyl group, a 2-thienylmethyl group, an alkoxymethyl group oran alkylthiomethyl group, or a salt of said cyclohexane compound, whichcomprises the steps of:

(a) reacting a compound of the formula (III): ##STR69## or a compound ofthe formula (IV): ##STR70## wherein R is as defined above and M' is analkali metal atom, with an organic acid chloride compound of the formula(V): ##STR71## wherein R¹ is as defined above, in an organic solventand/or water as the reaction medium in the presence or absence of a baseas an acid-binding agent to produce the compound of the formula (VI):##STR72## wherein R and R¹ are as defined above,

(b) subjecting the compound of the formula (VI) to an intermolecularrearrangement in the presence of a catalyst which is chosen from4-N,N-dimethylaminopyridine, 4-N,N-diethylaminopyridine,4-pyrolidinoaminopyridine, N-methylimidazole and N-ethylimidazole toproduce the compound of the formula (I): ##STR73## wherein R and R¹ areas defined above, and

(c) if desired, reacting the compound of the formula (I) with aninorganic or organic cation to produce the salt of the compound (I) withsaid inorganic or organic cation.

As an alternative, such new compounds of the formula (I) where R is analkyl group may be prepared by esterification of the corresponding freecarboxylic acid compound according to the following briefed reactionscheme: ##STR74## wherein R' represents an alkyl group and R¹ is asdefined hereinbefore in the formula (I).

Thus, the compound of the formula (If) can be produced by a methodcomprising the reaction of the compound of the formula (Ie) with ahalogenating agent in the presence or absence of a solvent and in thepresence or absence of a base as an acid-binding agent, followed by afurther esterification reaction of the acid halide derivative as formedwith an alkanol (R'OH) of the formula (VII) in the presence or absenceof a base. The reaction with the halogenating agent may be conducted ata temperature ranging from -20° C. to the boiling point of thehalogenating agent or of the solvent when used, and preferably at atemperature of from -10° C. to 100° C. for a period of 10 minutes to 7hours to give an acid halide derivative of the compound (Ie). Thehalogenating agent to be used for the above purpose may be thionylchloride, phosphorus trichloride, phosphorus pentachloride andphosphorus oxychloride. As the solvent which may be used for thehalogenation reaction, there may be mentioned dichloromethane,chloroform, carbon tetrachloride, benzene, toluene, xylene and the like.

The subsequent reaction of esterifying the acid halide derivative withthe alkanol (VII) may be carried out at a temperature of -20° C. to 100°C. for a time of 10 minutes to 48 hours. The base which is convenientlyused for the halogenation and esterification includes those which havegenerally been employed for the conventional dehydrohalogenation as theacid-binding agent in the art and may be selected from organic basessuch as triethylamine, pyridine, N,N-dimethylaminopyridine andN,N-dimethylaniline; and inorganic bases such as sodium hydroxide,potassium carbonate and sodium bicarbonate. The esterification with thealkanol (VII) may be conducted after or without separation of theintermediate acid halide derivative from the reaction medium.

The salts of the new cyclohexane compounds of the formula (I) or (Ia)according to this invention can be prepared as follows:

Thus, for example, an organic or inorganic salt of the new cyclohexanecompound may be produced by reacting in an organic solvent a compound ofthe general formula (I) or (Ia) with one or two or more equivalentproportions of a salt-forming reagent which is chosen from a primary,secondary or tertiary amine, a metal alcoholate, or a metal salt such asa chloride, sulfate, nitrate, acetate or carbonate; or hydride orhydroxide of a metal, for example, an alkali metal such as sodium,potassium; an alkaline earth metal such as calcium, magnesium, barium;aluminium, nickel, copper, manganese, cobalt, zinc, iron or silver. Whenthe compound (I) or (Ia) is reacted with one equivalent proportion ofthe salt-forming reagent, either the salt formed will be in the form ofthe salt of the general formula (Ib) as indicated in Table 2 when thegroup R or R² in the compound of the formula (I) or (Ia) is alkyl, orthe salt formed will be in the form of the salt of the general formula(Ic) as indicated in Table 3 when R or R² is hydrogen in the compound(I) or (Ia). If two or more equivalent proportions of the salt-formingreagent is reacted with the compound (I) or (Ia), the salt as formedwill take the form of the general formula (Id) as indicated in Table 4,when R or R² is a hydrogen atom in the compound (I) or (Ia).

The new compounds of the formula (I) or (Ia) according to this inventionmay possibly undergo a tautomerism and may be present in the form oftautomeric isomers as shown below, which fall within the scope of thisinvention. ##STR75## wherein Z denotes R or R² as defined hereinbeforeand Y denotes R¹ or R³ as defined hereinbefore.

Further, in an aqueous solution, the new compound salt of the formula(Ib) or (Ic) according to this invention may possibly change as shownbelow: ##STR76##

It may be added that when the cyclohexane compound of the formula (Ia)where R² is an alkyl group, is reacted with a primary, secondary ortertiary amine which may be represented by the formula ##STR77## whereR⁴, R⁵ and R⁶ are each as defined hereinbefore but all of R⁴, R⁵ and R⁶cannot be each a hydrogen atom simultaneously, there is formed such saltof the compound (Ia) which may be deemed as the substituted ammoniumsalt of the formula ##STR78## Further, when the cyclohexane compound ofthe formula (Ia) where R² is a hydrogen atom is reacted with a primary,secondary or tertiary amine of the formula (VIII), there is formed suchsalt of the compound (Ia) which may also be deemed as the substitutedammonium salt of the formula ##STR79##

In Tables 2-4, the salts of the new compounds with amine are representedas the type of the substituted ammonium salt as shown just above.

The plant-growth regulating effects of the new compounds of the generalformula (I) and the salts thereof are manifested predominantly as astunting or dwarfing effect on the vegetative growth of plants, butother various plant-growth regulating effects may be manifested bymodifying the nature of plants to be treated and the means, times andrates of application of the compounds or salts. Such plant-growthregulating effects which may be induced by the new compound of thisinvention include promotion of rooting, reduction in risk of lodging,promotion of sideshooting and root growth, maintenance of green color ofstems and leaves, promotion or delay of flowering, promotion of fruitingand ripening, and increase in resistances to temperature hindrance, tophytotoxicity caused by herbicides and to fungal or bacterial diseases.These various effects are not always manifested at a time.

The new compounds (including the salts) of this invention can controlinternode elongation of cereals and prevent or reduce lodging of rice,wheat, barley, maise and the other crop-plants by foliage and/orsoil-treatment. Application of the compound of this invention toseedlings of aquatic rice and growing vegetables can lead an improvementin quality, rooting after transplanting, and resistance to lowtemperature.

The foliage treatment with the new compound during the vegetative stageof crop plants, e.g. aquatic rice, wheat and barley also inducesshortening of top leaves or improvement in leaf orientation and henceincreases in light interception and utilization which will enhance theripening and increase the overall grain yield of such crop-plants.

Moreover, the compound of this invention may suppress spindly growth offlowers, ornamental plants and horticultural plants which may be causeddue to high temperature or sunshine shortage in plantation in agreenhouse.

The compound of the invention which exhibits the above-mentionedplant-growth regulating effects are very useful not only foragricultural and horticultural treatment but also for control of plantgrowth in non-crop lands. For instance, when the compound of thisinvention is applied onto lawns in park, playing field, golf link,airport or embankment or undergrowth grasses in orchard or pasture land,it is possible to inhibit the overluxuriant growth, to reduce the numberof reaping and/or to facilitate the mowing operations as usuallyrequired for maintenance. Further, application of the new compound ofthis invention onto swards can promote sideshooting and increase theplanting density of swards.

The compounds of this invention may be used as such for plant-growthregulating purposes but are more conveniently formulated intocompositions for such usage. According to a third aspect of thisinvention, there is thus provided a plant-growth regulating compositioncomprising a compound of the general formula (I) as hereinbefore definedor a salt thereof in combination with a carrier or diluent.

The invention also provides a method of regulating the growth of plant,which comprises applying an effective amount of a cyclohexane compoundof the formula (I) or a salt thereof of this invention to the foliage orseed of the plant to be treated or to the soil or locus where the plantto be treated is grown.

The compounds and salt can be applied in a number of ways, for example,they can be applied, formulated or unformulated, directly to the foliageof a plant, or they can be applied also to bushes and trees, to seeds orto other medium in which plants, bushes or trees are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as slow release granules.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dusting powders or granulescomprising the active ingredient and a solid diluent or carrier, forexample fillers such as kaolin, bentonite, dolomite, calcium carbonate,talc, powdered magnesia, Fuller's earth, gypsum, diatomaceous earth andChina clay.

The compositions may also be in the form of dispersible powders,granules or grains comprising a wetting agent to facilitate thedispersion in liquids of the powder or grains which may contain alsofillers and suspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving theactive ingredient(s) in an organic solvent optionally containingwetting, dispersing or emulsifying agent(s) and then adding the mixtureto water which may also contain wetting, dispersing or emulsifyingagent(s). Suitable organic solvents are kerosene, cyclohexanone,methylethyl ketone, acetone, methanol and acetonitrile.

The compositions may also be in the form of liquid preparations for useas dips or sprays which are generally aqueous dispersions or emulsionscontaining the active ingredient in the presence of one or more ofwetting agent(s), dispersing agent(s), emulsifying agent(s) orsuspending agent(s). These agents can be anionic or nonionic agents.

The compositions for use as aqueous dispersions or emulsions aregenerally supplied in the form of a concentrate containing a highproportion of the active ingredient(s), and the concentrate is to bediluted with water before use.

The plant-growth regulating composition of this invention may usually beformulated into a wettable powder comprising 5 to 95%, preferably 10 to50% by weight of the new compounds of this invention as activeingredient; 1 to 20%, preferably 5 to 10% by weight of surfactant; and 4to 44%, preferably 40 to 85% by weight of solid carrier.

The composition of this invention may be formulated into an emulsifiableconcentrate comprising 5 to 95%, preferably 20 to 70% by weight of thenew compound of this invention as active ingredient; 1 to 40%,preferably 5 to 20% by weight of surfactant; and 4 to 94%, preferably 10to 75% by weight of liquid carrier.

The composition of this invention may be made up as granules comprising0.5 to 40%, preferably 2 to 10% by weight of the new compound of thisinvention as active ingredient; 1 to 20%, preferably 2 to 10% by weightof surfactant; and 40 to 98.5%, preferably 80 to 96% by weight of solidcarrier. And, the composition of this invention may be formulated intodust comprising 0.5 to 10%, preferably 1 to 5% by weight of the activeingredient; and 99.5 to 90%, preferably 99 to 95% by weight of finelydivided solid carrier.

The composition of this invention may also be formulated into a pastecomprising 0.1 to 20%, preferably 1 to 10% by weight of the activeingredient, 1 to 20%, preferably 2 to 10% by weight of surfactant; and60 to 98.9%, preferably 80 to 97% by weight of paste base.

The rate of application of the new compounds of this invention for usein the purposes of plant-growth regulation will normally depend onvarious factors, including nature of plants to be treated, applicationtime and application means. In general, however, the rate of applicationmay be in the range of 0.01 kg to 50 kg per hectare and preferably of0.05 kg to 10 kg per hectare as the active ingredient.

For the purpose of preventing or reducing lodging of crop plants such aswheat, the rate of application may desirably be in a range of 0.1 kg to1 kg per hectare as the active ingredient. For the purpose ofsuppressing the growth of swards in non-crop lands orundergrowth-grasses in orchards, the rate of application may be in arange of 0.5 kg to 5 kg per hectare as the active ingredient. For thepurpose of regulating the growth of aquatic rice plants, the rate ofapplication may be in the range of 0.5 kg to 5 kg per hecatre as theactive ingredient when it is applied to the soil, and the formulationsto be applied to the foliage of aquatic rice plant may contain theactive ingredient at a concentration of 100 ppm to 5000 ppm. In general,the composition of this invention may be formulated into a diluted ordilutable preparation containing the active ingredient at aconcentration of 10 ppm to 10,000 ppm and preferably of 100 ppm to 5000ppm for use in the foliage treatment.

This invention is now illustrated with reference to the followingExamples to which this invention is not limited.

EXAMPLE 1

Preparation of Compound No. 15, namely ethyl3,5-dioxo-4-butyrylcyclohexanecarboxylate.

To 150 ml of ethanol containing 3.4 g of sodium was added dropwise 31 gof diethyl acetonylsuccinate (or diethyl acetmethylsuccinate) over aboutone hour with stirring at ambient temperature. The mixture was heatedunder reflux for 2 hours and then cooled to room temperature, followedby distillation off of the ethanol under reduced pressure. There wasthus obtained a brown viscous liquid comprising sodium salt of ethyl3,5-dioxocyclohexanecarboxylate as formed, to which were added 100 ml oftoluene, 50 ml of ice water and 0.3 g of γ-picoline and then addeddropwise 15 g of n-butyryl chloride at ambient temperature underagitation over about 2 hours. The resultant reaction mixture wasagitated for further 30 minutes and then the toluene layer wasseparated, washed with water, dried and admixed with 0.8 g of4-N,N-dimethylaminopyridine. The admixture was heated with agitation ata temperature of 80°-90° C. for 3 hours. The toluene was then distilledoff from the reaction solution under reduced pressure and the residuewas chromatographed on a column of silica gel developed with benzene togive 19.5 g (55.9%) of the object compound (Compound No. 15).

Compound Nos. 1, 2 and Nos. 4-44 could be prepared by the same procedureas described in Example 1.

EXAMPLE 2

Preparation of Compound No. 26, namely ethyl3,5-dioxo-4-n-valerylcyclohexanecarboxylate.

2.1 g of 5-ethoxycarbonyl-cyclohexane-1,3-dione, namely ethyl3,5-dioxocyclohexanecarboxylate was dissolved in 20 ml ofdichloromethane, to which was added 1.7 g of triethylamine and thenadded dropwise 1.9 g of n-valeryl chloride with stirring over 30minutes. The mixture was continued to be stirred for 3 hours, and thereaction solution obtained was washed with water. The organic layer wasseparated from the aqueous phase, dried and concentrated to a smallvolume.

The concentrated solution was taken up in 20 ml of toluene, followed byaddition of 0.6 g of 4-N,N-dimethylaminopyridine and heating at atemperature of 80°-90° C. for 4 to 5 hours. Subsequently, the toluenewas removed from the reaction solution by distillation under reducedpressure, and the residue was chromatographed on silica gel usingbenzene as the developing solvent to yield 2.2 g (71.9%) of the aimedcompound (Compound No. 26).

Compound Nos. 1-25 and Nos. 27-44 could be produced by the sameprocedure as stated in Example 2.

EXAMPLE 3

Preparation of Compound No. 51 (see Table 2)

1.0 g of ethyl 3,5-dioxo-4-propionylcyclohexanecarboxylate was dissolvedin 20 ml of chloroform, to which was then added 1.0 g of diethylamine asthe salt-forming reagent. The mixture was allowed to stand at roomtemperature for two hours, after which the chloroform and the excess ofdiethylamine were distilled off from the reaction solution under reducedpressure to yield 1.3 g of the object compound (Compound No. 51) as apale brown solid and represented by the formula: ##STR80##

EXAMPLE 4

Preparation of Compound No. 54 (see Table 2)

4.0 g of ethyl 3,5-dioxo-4-propionylcyclohexanecarboxylate was dissolvedin 50 ml of ethanol and 1.7 g of diethanolamine was added to thesolution, followed by stirring for 30 minutes. The ethanol was thendistilled off from the reaction solution under reduced pressure toprecipitate a crystal, which was washed with ethyl ether and dried toafford 5.2 g of the object compound as a pale yellow crystal having amelting point of 76°-78° C.

EXAMPLE 5

Preparation of Compound No. 63

1.0 g of triethylamine was added to 1.0 g of ethyl3,5-dioxo-4-propionylcyclohexanecarboxylate dissolved in 20 ml ofchloroform, and the resultant mixture was allowed to stand at ambienttemperature for 2 hours. The chloroform and the excess triethylaminewere distilled off from the reaction solution under reduced pressure toyield 1.4 g of the desired compound (Compound No. 63) in the form ofbrown viscous liquid with a refractive index n_(D) ²⁰ =1.5098.

EXAMPLE 6

Preparation of Compound No. 73

1.0 g of potassium salt of ethyl3,5-dioxo-4-propionylcyclohexanecarboxylate was dissolved in water, towhich was added 0.25 g of calcium chloride. The mixture was allowed tostand overnight to effect the cation-exchange reaction, after which thereaction solution was concentrated by evaporation of the water. Theconcentrated solution was extracted with hot ethanol and the ethanolicextract was admixed with hexane to precipitate a crystal. The latter wasfiltered and dried to give 0.7 g of the aimed compound as a colorlesspowder having a melting point of 213°-215° C.

EXAMPLE 7

Preparation of Compound No. 74

To 8.4 g of ethyl 3,5-dioxo-4-propionylcyclohexanecarboxylate dissolvedin 80 ml of ethyl ether was added dropwise under agitation at roomtemperature 50 ml of ethanolic solution containing 1.4 g of sodiumhydroxide. After completion of the addition, the precipitated crystalwas collected by filtration and dried. Recrystallization from a mixedsolvent of ethanol and hexane gave 7.2 g of the desired sodium saltcompound as colorless needles with a melting point of 178.5°-179.5° C.

EXAMPLE 8

Preparation of Compound No. 78

2.0 g of ethyl 4-butyryl-3,5-dioxo-cyclohexanecarboxylate was added intoethanol containing 0.53 g of sodium ethylate, and the mixture wasallowed to stand at room temperature for 3 hours. The ethanol was thendistilled off from the reaction solution under reduced pressure to yield2.17 g of the desired sodium salt as a pale yellow amorphous solid.

EXAMPLE 9

Preparation of Compound No. 84 (see Table 3)

1.3 g of 4-butyryl-3,5-dioxo-cyclohexanecarboxylic acid was dissolved in20 ml of methanol and 0.58 g of triethylamine was added to the solution.The mixture was allowed to stand overnight at ambient temperature, afterwhich the methanol was removed from the reaction solution by evaporationunder reduced pressure to leave 1.8 g of the object compound (CompoundNo. 84) as a pale yellow viscous liquid with n_(D) ²⁰ =1.5182.

The above procedure was repeated using choline in place of thetriethylamine to give Compound No. 85.

EXAMPLE 10

Preparation of Compound No. 87

1.0 g of 4-butyryl-3,5-dioxo-cyclohexanecarboxylic acid was dissolved in20 ml of methanol and 0.4 g of diethanolamine (HOCH₂ CH₂)₂ NH was addedto the solution. The mixture was allowed to stand at room temperaturefor 3 hours and the methanol was then removed from the reaction solutionby evaporation under reduced pressure to give 1.4 g of the desiredcompound as a pale brown viscous liquid with n_(D) ²⁰ =1.5330. Thisproduct was of the formula: ##STR81##

EXAMPLE 11

Preparation of Compound No. 91

0.84 g of sodium bicarbonate was added to 2.1 g of3,5-dioxo-4-propionylcyclohexanecarboxylic acid dissolved in 30 ml ofethanol, and the mixture was heated under reflux for 3 hours. Thereaction solution was then cooled and filtered to leave a crystal, whichwas recrystallized from ethanol to give 2.2 g of the desired compound aspale yellow flakes with a melting point of 225° C. (decomp.).

EXAMPLE 12

Preparation of Compound No. 93 (see Table 4)

1.4 g (6.6 m moles) of 3,5-dioxo-4-propionylcyclohexanecarboxylic acidwas dissolved in 30 ml of ethanol, and 0.7 g (6.6 m moles) of anhydroussodium carbonate was added to the solution. The resultant mixture washeated under reflux for 6 hours, after which the reaction solution wascooled and filtered to leave a crystal. Recrystallization of the crystalfrom a mixed solvent of ethanol, methanol and hexane gave 1.3 g of thedesired di-sodium salt compound as a pale yellow powder having a meltingpoint of 240° C. (decomp.).

EXAMPLE 13

Preparation of Compound No. 95

2.0 g of 4-butyryl-3,5-dioxo-cyclohexanecarboxylic acid was dissolved ina mixture of methanol and water (1:1), to which was then added 0.72 g ofsodium hydroxide. After complete dissolution of the latter, theresulting solution was allowed to stand overnight, followed by removalof the methanol and water by distillation under reduced pressure. Therewas thus obtained 2.4 g of the object compound as a redish brown viscousliquid with n_(D) ²⁰ =1.5261.

EXAMPLE 14

Preparation of ethyl 3,5-dioxo-4-propionylcyclohexanecarboxylate

4.2 g of ethyl 3,5-dioxocyclohexanecarboxylate and 3.4 g oftriethylamine were dissolved in 50 ml of dichloromethane, to which wasadded dropwise 2.9 g of propionyl chloride under stirring at roomtemperature. The resultant mixture was allowed to react at ambienttemperature for 2 hours, after which the reaction solution was washedwith water and admixed with a dilute aqueous sodium bicarbonate solutionto remove the acidic matters from the reaction solution. The organiclayer was then separated from the aqueous phase, dried and concentratedto a small volume. The concentrated solution was taken up in 20 ml oftoluene, followed by addition of 0.5 g of 4-N,N-dimethylaminopyridineand heating the mixture at 85° C. for 3 hours. Thereafter, the toluenewas removed from the reaction solution by distillation under reducedpressure, and the residue was chromatographed on silica gel usingbenzene as developing solvent to afford 2.5 g of the title compound(Compound No. 9 of Table 1) as colorless flakes having a melting pointof 55°- 56° C.

EXAMPLE 15

Preparation of ethyl 4-n-butyryl-3,5-dioxocyclohexanecarboxylate

28.8 g of sodium salt of ethyl 3,5-dioxocyclohexane carboxylate wasadmixed with 100 ml of toluene and 50 ml of ice water, and to theresulting suspension was added 0.3 g of γ-picoline. To the mixtureobtained was added dropwise 15 g of n-butyryl chloride with stirringover about two hours, and the resultant mixture was continued to bestirred for 30 minutes. The toluene layer was then separated from theaqueous phase, dried and concentrated to a small volume. Theconcentrated solution was dissolved in 20 ml of toluene and 0.8 g of4-N,N-dimethylaminopyridine was added to the solution, which was thenheated at 80°-90° C. under agitation for 3 hours. Thereafter, thetoluene was removed from the reaction solution by distillation underreduced pressure, and the residue was chromatographed on silica geldeveloping with benzene to yield 19.5 g of the title compound (CompoundNo. 15 of Table 1) as pale yellow prisms with a melting point of 34°-35°C.

The following Examples 16-20 illustrate the preparation of thecompositions according to this invention, in which parts are all byweight.

EXAMPLE 16

Wettable powder

A composition in the form of wettable powder was prepared by mixinghomogeneously and grinding 10 parts of Compound No. 1, 85 parts ofkieselguhr, 2 parts of sodium dinaphthylmethanesulfonate and 3 parts ofsodium lignosulfonate.

A similar wettable powder was produced by the same procedure as abovebut using Compound No. 45 instead of Compound No. 1.

EXAMPLE 17

Emulsifiable concentrate

An emulsifiable concentrate was made up by mixing the ingredients, andstirring the mixture until all the constituents were dissolved.

Compound No. 15: 30 parts

Cyclohexane: 20 parts

Polyoxyethylenealkylaryl ether: 11 parts

Calcium alkylbenzenesulfonate: 4 parts

Methylnaphthalene: 35 parts

A similar emulsifiable concentrate was prepared by the same procedure asdescribed above but replacing Compound No. 15 by Compound No. 46.

EXAMPLE 18

Grains

A composition in the form of grains was prepared by uniformly mixing andgrinding together 5 parts of Compound No. 13, 2 parts of sodiumlaurylsulfate, 5 parts of sodium lignosulfonate, 2 parts ofcarboxymethylcellulose and 86 parts of clay, followed by addition of 20parts of water per 80 parts of the mixture. The resultant mixture wasmilled and formulated into grains of 14-32 mesh size by means of anextrusion granulator.

A similar granular composition was made up by repeating the aboveprocedure but replacing Compound No. 13 by Compound No. 47.

EXAMPLE 19

Dusting powder

4 parts of Compound No. 16, 5 parts of kieselguhr and 91 parts of claywere homogeneously mixed and ground together to formulate into a dustingpowder.

The above procedure was repeated using Compound No. 48 instead ofCompound No. 16 to produce a similar dusting powder.

EXAMPLE 20

Paste formulation

A paste formulation was prepared by mixing uniformly 5 parts of CompoundNo. 9, 1 part of xylene, 5 parts of polyoxyethylenesorbitan monolaurateand 89 parts of white vaseline as paste base.

A similar paste formulation was made up by the same procedure asmentioned above except that Compound No. 9 was replaced by Compound No.49.

The following Examples illustrate the plant-growth regulating effects ofthe compounds according to this invention.

EXAMPLE 21

This Example illustrates the retardation effect of the compounds of thisinvention on the growth of aquatic rice plants.

Aquatic rice plants ("Kinmage" Variety) at the twoleaf stage weretreated with the compounds of this invention under test. Thus, thecompounds were formulated into a wettable powder as prepared in Example16 and the wettable powder was diluted with such a volume of water that1000 l of the diluted aqueous preparations as sprayed gave the rate ofapplication of 1 kg of the active ingredient per hectare upon thefoliage treatment by spraying.

On the day of the application and 3 weeks after the application of thecompounds, the length of stems and leaves of the treated plants weremeasured, and retardation of growth was calculated by the followingequation: ##EQU1##

A=(Foliar length in untreated plots 3 weeks after application)--(Foliarlength in untreated plots on the day of application)

B=(Foliar length in treated plots 3 weeks after application)--(Foliarlength in treated plots on the day of application)

The test results are set out in Table 6 below.

                  TABLE 6                                                         ______________________________________                                        Compound  Retardation Compound    Retardation                                 No. tested                                                                              (%)         No. tested  (%)                                         ______________________________________                                         1        57          50          44                                           2        58          51          61                                           3        57          52          60                                           4        64          53          62                                           5        67          54          64                                           6        52          55          63                                           7        49          56          60                                           8        67          57          62                                           9        71          58          59                                          10        78          59          65                                          11        65          60          64                                          12        74          61          65                                          13        68          62          60                                          14        59          63          57                                          15        82          64          60                                          16        79          65          65                                          17        56          66          63                                          18        58          67          62                                          19        66          68          70                                          20        69          69          66                                          21        77          70          67                                          22        63          71          64                                          23        62          72          71                                          24        63          73          66                                          25        81          74          72                                          26        55          75          70                                          27        56          76          62                                          28        49          77          65                                          29        41          78          59                                          30        30          79          63                                          31        22          80          57                                          32        61          81          72                                          33        63          82          69                                          34        58          83          66                                          35        57          84          70                                          36        76          85          49                                          37        74          86          58                                          38        62          87          58                                          39        61          88          61                                          40        53          89          68                                          41        54          90          57                                          42        58          91          73                                          43        57          92          70                                          44        61          93          65                                          45        53          94          71                                          46        63          95          67                                          47        65          CCC          0                                                                (Comparative)                                           48        52          B-Nine       0                                                                (Comparative)                                           49        46          MH          41                                                                (Comparative)                                           ______________________________________                                    

The results of Table 6 indicate that rice plant height can be controlledby the application of the new compounds of this invention and thusspindly growth of rice plant can be prevented.

EXAMPLE 22

This Example illustrates the stunting effect of the compounds of thisinvention on the growth of grass swards.

Creeping bentgrass (Agrostis stolonifera) ("Seaside" Variety) andJapanese lowngrass (Zoysia japonica) of 2 cm in height were sprayed withthe diluted aqueous preparations containing the compounds of thisinvention. The diluted aqueous preparations as used were prepared byformulating the compounds into wettable powder as in Example 16 anddiluting the wettable powder with such a volume of water that 1000 l ofthe diluted aqueous preparations as sprayed gave the rate of applicationof 1 kg of the active ingredient per hectare upon the foliage treatmentby spraying.

5 Weeks after application of the compounds, assessment was made andpercentage of retradation was calculated in the same way as described inExample 21. Phytotoxicity was also assessed for some of the testcompounds and indicated by the following scales:

    ______________________________________                                        Scales          Degree of Phytotoxicity                                       ______________________________________                                        -               Not detected                                                  ±            Small                                                         +               Middle                                                        ++              Great                                                         +++             Kill                                                          ______________________________________                                    

The test results are shown in Tables 7a and 7b below.

                  TABLE 7a                                                        ______________________________________                                        Compound   Retardation (%)                                                    No. tested Creeping bentgrass                                                                          Japanese lowngrass                                   ______________________________________                                         1         --            38                                                    9         65            65                                                   13         70            71                                                   15         62            63                                                   16         --            42                                                   17         --            40                                                   18         --            54                                                   25         60            75                                                   ______________________________________                                    

                  TABLE 7b                                                        ______________________________________                                        Retardation (%)     Phytotoxicity                                             Compound                                                                              Creeping Japanese   Creeping                                                                             Japanese                                   No. tested                                                                            bentgrass                                                                              lowngrass  bentgrass                                                                            lowngrass                                  ______________________________________                                        46      45       68         -      -                                          54      51       58         -      -                                          74      53       59         -      -                                          90      49       54         -      -                                          94      40       43         -      -                                          MH (Com-                                                                              -        37         ++     +                                          parative)                                                                     ______________________________________                                    

From the results of Tables 7a and 7b as above, it will be seen that thenew compounds and salts of this invention exert the stunting or dwarfingeffects on lawn grasses for a long period without significant phytotoxiceffects and without deteriously affecting the appearance (particularlythe color) of the grass, so that the compounds of this invention areuseful to reduce the need for mowing the grass swards.

EXAMPLE 23

This Example illustrates the improvements in quality of rice seedlingsby application of the compounds of this invention.

Emergent seeds of aquatic rice ("Kinmaze" Variety) were sown in arice-planting case of 30×60 cm in size, then covered with soil andirrigated with water. The compounds under test were formulated into anemulsifiable concentrate as stated in Example 17 which was then dilutedwith water so that the diluted emulsions contained the active ingredientat the concentrations as indicated in Table 8 below. The dilutedemulsions so formulated were sprayed onto the soil surface at the rateof 20 ml per case. The cases were then kept in a thermostatic chamber at30° C. for 3 days and further placed in a greenhouse. When the riceseedlings in untreated plots had reached the stage of 2.5 leaf age, theheight of seedlings, leaf age and dry weights of the foliage parts(stems/leaves) and roots of the treated and untreated plants weremeasured. Some members of the seedlings were washed with water, and thenthe seedlings were transplanted into and placed at an angle of 45° in apot flooded with water to 2 cm depth, after cutting the roots into theconstant length of 2 cm. 10 Days later, the rising angle of theseedlings and the chlorophyll content of their second leaf weredetermined.

The results are shown in Table 8 below, where the assessment particularsother than the rising angle are indicated in terms of the percentagesbased on the results obtained for the untreated plots.

It will be seen from Table 8 that the compounds of this invention cansuppress the excessive growth of rice seedlings in a planting case,promote the growth of roots and accelerate the rooting of transplantedrice seedlings.

                                      TABLE 8                                     __________________________________________________________________________    Concentration                        Quality of rice seedling 10 days         (ppm) of active                                                                             Quality of rice seedling at the time transplantation                                                 after transplantation                          ingredient in      Dry weight                                                                          Dry weight                                                                          Raising  Chlorophyll                     Compound                                                                            the sprayed                                                                           Plant Leaf age                                                                           of foliage                                                                          of root                                                                             angle of content of                      No. tested                                                                          emulsion                                                                              height (%)                                                                          (%)  parts (%)                                                                           parts (%)                                                                           seedling (degree)                                                                      second leaf                     __________________________________________________________________________                                                  (%)                             15    4000    59    100  92    113   90       111                                   2000    67    100  97    119   90       110                                   1000    88    100  101   120   87       108                             54    1000    83    104  98    110   90       113                             55    1000    80    108  96    115   90       120                             57    1000    85    104  98    112   90       112                             70    1000    79    108  96    119   90       136                             87    1000    76    108  94    119   90       139                             93    1000    83    104  97    112   90       118                             Untreated                                                                           --      100   100  100   100   75       100                             __________________________________________________________________________

EXAMPLE 24

This Example illustrates the suppressive effect of the compounds of thisinvention on internode elongation of aquatic rice plants.

3 hills (each hill comprising two seedlings) of aquatic rice seedlings("Kinmaze" Variety) at the 3 leaf stage were transplanted in a 1/2000are Wagner pot. 35 Days after transplanting, a dilute aqueous emulsioncontaining the test compound which had been prepared by diluting withwater an emulsifiable concentrate formulated as in Example 17 was addeddropwise into the flooding water in the pot at an application rate of 1kg of the active ingredient per hectare.

3 Months after the application, assessments were made on the stemlength, length of each of the first to fifth internodes and weight ofeach unit internode. The test results are indicated in Table 9 in termsof the percentages based on those in the untreated plots. The "unitinternode weight" means dry weight of the internode of 1 cm long.

                                      TABLE 9                                     __________________________________________________________________________    Compound                                                                      No.   Stem                                                                              Each internode length                                                                           Unit internode weight                             tested                                                                              length                                                                            First                                                                            Second                                                                            Third                                                                             Fourth                                                                            Fifth                                                                            First                                                                            Second                                                                            Third                                                                             Fourth                                                                            Fifth                              __________________________________________________________________________    15    87  98 91  63  68  59 106                                                                              108 114 120 123                                __________________________________________________________________________

From the results of Table 9 as above, it will be seen that the newcompounds of this invention exert the stunting effects on the elongationof the lower (third to fifth) internodes of aquatic rice plants and makethese lower internodes thick and strong, so that the compounds areuseful to reduce the risk of lodging of aquatic rice plants.

EXAMPLE 25

This Example illustrates that the compounds of this invention reduce therisk of lodging of wheat plants.

Seeds of wheat ("Norin" No. 61 Variety) were sown in a field. When thewheat plants were grown to a stage of 30 to 40 cm in height, the fieldwas divided into several plots each of 10 m² area. The wheat plants ineach plot were treated by spraying their foliage evenly with a dilutedaqueous preparations which had been prepared by formulating thecompounds of this invention into a wettable powder as stated in Example16 and diluting the wettable powder with such a volume of water that 500litres of the diluted aqueous preparations so sprayed gave the rates ofapplication of active ingredient as indicated in the following Table 10.For comparison purpose, 2-chloroethyl trimethyl ammonium chloride (CCC,known as chlormequat) was tested in the same manner as above.

80 Days after the treatment, the length of stem of the wheat plants andthe extent of lodging were evaluated. The results obtained are tabulatedin Table 10 below.

                  TABLE 10                                                        ______________________________________                                                  Rate of application                                                                         Stem                                                  Compound No.                                                                            of active ingredient                                                                        length                                                tested    (kg per hectare)                                                                            (%)     Extent of lodging                             ______________________________________                                         9        0.2           83      Very slight                                             0.4           76      None                                          15        0.2           80      Very slight                                             0.4           75      None                                          25        0.2           83      Very slight                                             0.4           77      None                                          37        0.2           85      Slight                                                  0.4           80      Very slight                                             0.5           101     None                                          CCC       1.0           81      Slight                                        (comparative)                                                                           2.0           77      Very slight                                   Untreated --            100     Medium to great                               ______________________________________                                    

EXAMPLE 26

This Example demonstrates that the salts of the cyclohexane compounds ofthe formula (Ia) according to this invention have reduced influences oneyes in contact with the latter.

3 Rabbits (Female, "Japan White" Variety, 4 months-age) of whicheyeballs were found to suffer from no damage by a check with 5% aqueousfluorescein sodium solution were fixed on a fixing table. 100 mg of thetest compounds as such were dropped into the left eyes of the rabbitsand their eyelids were closed for one seconds, after which the rabbitswere placed in a breeding case. The right eyes were remaining untreatedfor control. Eye-examinations were made 24 hours and 2, 3, 4, 7, 14 and21 days after the treatment. The stimulus responses were evaluated inrespect of various observations as indicated in Table 11, and theresults are set out in Table 12.

TABLE 11

Cornea

(A) Opacity-Turbidity (the most opaque region of cornea was examined)were estimated by the following scales:

Scale 1 . . . Sporadical or diffusive opacity occurred to such extentthat iris still remained clearly visible.

Scale 2 . . . Opacity occurred to such extent that fine parts of iriswere somewhat dimly visible.

Scale 3 . . . Opacity occurred to such extent that fine parts of iriswere indistinct and the size of pupil is visually distinguishable withdifficulty.

Scale 4 . . . Opacity occurred to such extent that iris was not visible.

(B) Area suffering from corneal damage (denoted as "Area" below) wasscaled as follows:

Scale 1 . . . 0<"Area"<1/4

Scale 2 . . . 1/4≦"Area"<1/2

Scale 3 . . . 1/2≦"Area"<3/4

Scale 4 . . . 3/4≦"Area"

A value of a product of scale (A)×scale (B)×5 was calculated andindicated as "Evaluation scores" of stimulus to cornea in the followingTable 12, but this calculated value did not extend over the maximumvalue 80 even for the worst case.

Iris

(A)

Scale 1 . . . one or more signs of acceleration of wrinkle formation,hyperemia, swelling and hyperemia of corneal surroundings in iris weredetectable but reflection response of iris to light was still good.

Scale 2 . . . one or more signs of no reflection response of iris tolight, bleeding and wide-spread breakdown were detectable.

A value of a product of scale (A)×5 was calculated and indicated as"Evaluation scores" of stimulus to iris in Table 12, but this calculatedvalue did not extend over the maximum value 10 even for the worst case.

Conjunctiva

(A) Redness (only the redness developed in the eyelid conjunctiva wasexamined.)

Scale 1 . . . Acceleration of hyperemia was observed.

Scale 2 . . . Wide-spread, deep-color redness and difficulty inidentification of vasa were observed.

Scale 3 . . . Wholly-spread, deep-color redness was observed.

(B) Chemosis

Scale 1 . . . Acceleration of chemosis (including nictitating membrane)was observed.

Scale 2 . . . Swelling associated with partial valgum of eyelid wasobserved.

Scale 3 . . . Eyelid closing (in about half region) associated withswelling was observed.

Scale 4 . . . Eyelid closing (about half to whole region) with swellingwas observed.

(C) Secreta

Scale 1 . . . More than ordinary amount (excluding the small quantity ofsecreta usually observed in inner canthus of heathy animal) of secretawas observed.

Scale 2 . . . Secreta was formed in the amount to wet and stain eyelidand also hairs contact with eyelid.

Scale 3 . . . Secreta was formed in the amount to wet and stain eyelidand also the eye surroundings over a fairly wide region.

A value of a product of [scale (A)+scale (B)+scale (C)]×2 was calculatedand indicated as "Evaluation scores" in term of secreta in Table 12, butthis calculated value did not extend over the maximum value 20 for theworst case.

                                      TABLE 12                                    __________________________________________________________________________                       Compound No. tested                                                           Compound                                                                            Compound                                                                            Compound                                                                            Compound                                                                            Compound No. 9                                  Body  No. 54                                                                              No. 74                                                                              No. 93                                                                              No. 94                                                                              (comparative)                                   weight (kg)                                                                         2.5                                                                             2.6                                                                             2.5                                                                             2.7                                                                             3.0                                                                             2.7                                                                             3.0                                                                             2.6                                                                             2.5                                                                             2.5                                                                             2.5                                                                             2.1                                                                             2.7                                                                              2.6                                                                              2.6                          __________________________________________________________________________    Evaluation                                                                          Cornea 24 hours                                                                            0 0 0 0 5 0 0 0 0 0 0 0 20 15 20                           Scores       2 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 20 15 20                           of           3 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 20 10 15                           stimulus     4 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 20 10 20                                        7 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 20 5  5                                         14 days                                                                             0 0 0 0 0 0 0 0 0 0 0 0 5  0  0                                         21 days                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         Average 0     0.2   0     0      11.4                                  Iris   24 hours                                                                            0 0 0 0 5 0 0 0 0 0 0 0 5  0  0                                         2 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 5  0  0                                         3 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 5  0  0                                         4 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         7 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         14 days                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         21 days                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         Average 0     0.2   0     0       0.7                                  Conjunctiva                                                                          24 hours                                                                            4 2 2 2 4 2 6 4 6 0 0 0 8  8  6                                         2 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 6  4  4                                         3 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 2  0  0                                         4 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 2  0  0                                         7 days                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         14 days                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         21 days                                                                             0 0 0 0 0 0 0 0 0 0 0 0 0  0  0                                         Average 0.4   0.4   0.8   0      1.9                             __________________________________________________________________________

What we claim is:
 1. A cycohexane compound of the general formula:##STR82## wherein R represents a hydrogen atom or an alkyl group, analkylthioalkyl group of a phenyl group, a (C₁ -C₄)alkylphenyl group, ahalophenyl group or a (C₁ -C₄)alkoxyphenyl group and R¹ represents analkyl group, a benzyl group, a (C₁ -C₄)alkylbenzyl group, a halo-benzylgroup or a (C₁ -C₄)alkoxybenzyl group, a phenethyl group, aphenoxymethyl group, a 2-thienylmethyl group, an alkoxy-methyl group oran alkylthiomethyl group, or a salt of said cyclohexane compound.
 2. Acompound according to claim 1 in which R is a hydrogen atom or an alkylgroup.
 3. A compound according to claim 1 in which R¹ is an alkyl group.4. A compound according to claim 1 in which both R and R¹ are each analkyl group of 1-8 carbon atoms.
 5. A compound according to claim 1 inwhich R is an alkyl group which is chosen from methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl and isopentyl.
 6. A compound according toclaim 1 in which R¹ is an alkyl group which is chosen from methyl,ethyl, n-propyl, isopropyl.
 7. A compound according to claim 1 which isselected from 3,5-dioxo-4-propionylcyclohexanecarboxylic acid methylester; 3,5-dioxo-4-propionylcyclohexanecarboxylic acid ethyl ester;3,5-dioxo-4-propionylcyclohexanecarboxylic acid n-propyl ester;3,5-dioxo-4-butyrylcyclohexanecarboxylic acid;3,5-dioxo-4-butyrylcyclohexanecarboxylic acid ethyl ester;3,5-dioxo-4-butyrylcyclohexanecarboxylic acid n-propyl ester;3,5-dioxo-4-butyrylcyclohexanecarboxylic acid isopropyl ester;3,5-dioxo-4-butyrylcyclohexanecarboxylic acid n-butyl ester;3,5-dioxo-4-butyrylcyclohexanecarboxylic acid isopentyl ester;3,5-dioxo-4-isobutyrylcyclohexanecarboxylic acid ethyl ester; and3,5-dioxo-4-acetylcyclohexanecarboxylic acid.
 8. A compound as claimedin claim 1, which is a salt of a cyclohexane compound of the generalformula: ##STR83## wherein R² represents a hydrogen atom or an alkylgroup and R³ represents an alkyl group.
 9. A compound according to claim8 which is a salt of the cyclohexane compound of the formula (Ia) withan inorganic cation which is selected from cations of an alkali metal,an alkaline earth metal, aluminum, nickel, copper manganese, cobalt,zinc, iron and silver, as well as ammonium cation.
 10. A compoundaccording to claim 8 which is a salt of the cyclohexane compoundrepresented by the general formula: ##STR84## wherein R² and R³ are asdefined in claim 8 and M represents an inorganic cation which isselected from cations of an alkali metal, an alkaline earth metal,aluminum, nickel, copper, manganese, cobalt, zinc, iron and silver andamminium cation.
 11. A compound according to claim 8 which is a salt ofthe cyclohexane compound represented by the general formula: ##STR85##wherein R³ is as defined in claim 8 and M represents an inorganic cationwhich is selected from cations of an alkali metal, an alkaline earthmetal, aluminum, nickel, copper, manganese, cobalt, zinc, iron andsilver and amminium cation.
 12. A compound according to claim 8 which isa salt of the cyclohexane compound represented by the general formula:##STR86## wherein R³ is as defined in claim 8 and M represents aninorganic cation which is selected from cations of an alkali metal, analkaline earth metal, aluminum, nickel, copper, manganese, cobalt, zinc,iron and silver and amminium cation.
 13. A compound according to claim 8which is a salt of the cyclohexane compound of the formula (Ia) with anorganic cation which is a substituted ammonium cation, the substituenton the ammonium cation being a benzyl, a halobenzyl, pyridyl, analkylpyridyl, or a polymethylene link optionally interrupted by anoxygen atom.
 14. A compound according to claim 8 which is chosenfrom:sodium salt of ethyl 3,5-dioxo-4-propionyl-cyclohexanecarboxylate;and disodium salt of 3,5-dioxo-4-propionyl-cyclohexanecarboxylic acid.15. A compound of the formula ##STR87## wherein R is an alkyl group andR¹ is an alkyl group, or a salt of said cyclohexane compound.
 16. Acompound according to claim 15 which is3,5-dioxo-4-propionylcyclohexanecarboxylic acid ethyl ester.
 17. Acompound of the formula ##STR88## wherein R is phenyl, a (C₁ -C₄alkylphenyl, a halo-phenyl or a (C₁ -C₄)alkoxyphenyl group, and R¹ is analkyl group or a salt of said cyclohexane compound.
 18. A compound ofthe formula ##STR89## wherein R is an alkylthioalkyl group and R¹ is analkyl group or a salt of said cyclohexane compound.
 19. A compound ofthe formula. ##STR90## wherein R is an alkyl group and R¹ is benzyl a(C₁ -C₄)alkylbenzyl, a halo-benzyl, a (C₁ -C₄)alkoxybenzyl, phenethyl,phenoxymethyl, 2-thienylmethyl, an alkoxymethyl or an alkylthiomethylgroup or a salt of said cyclohexane compound.
 20. A plant-growthregulating composition comprising as active ingredient an amounteffective to regulate plant growth of a cyclohexane compound of thegeneral formula: ##STR91## wherein R represents a hydrogen atom or analkyl group, an alkylthioalkyl group or a phenyl group, a (C₁-C₄)alkylphenyl group, a halophenyl group or a (C₁ -C₄)alkoxyphenylgroup; and R¹ represents an alkyl group, a benzyl group, a (C₁-C₄)alkylbenzyl group, a halo-benzyl group or a (C₁ -C₄)alkoxybenzylgroup, a phenethyl group, a phenoxymethyl group, a 2-thienylmethylgroup, an alkoxy-methyl group or an alkylthiomethyl group, or a salt ofsaid cyclohexane compound in association with an inert carrier for theactive ingredient.
 21. A method of regulating the growth of plant, whichcomprises applying an effective amount of a cyclohexane compound of theformula (I) or a salt thereof as claimed in claim 1 to the foliage orseed of the plant to be treated or to the soil or locus where the plantto be treated is grown.